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A STUDY  OF  THE  PRODUCTS  GOAL 
OBTAINED  BY  THE  USE  OF 
BENZENE  AND  TOLUENE 
UNDER  HIGH  PRESSURE 

BY 


FRANKLIN  A.  McCANN 


THESIS 


FOK  THE 


D E G K K E O F B A C H E I . OR  OF  SCIENCE 


COLLKGK  OF  LIBERAL  ARTS  AND  SCIENCES 


UNLVEKSITY  OF  ILLINOIS 


€ ■* 


Finley 


UNIVERSITY  OF  ILLINOIS 


May ^3^ ig^ 

THIS  IS  TO  CERTIFY  THAT  THE  THESIS  PREPARED  UNDER  MY  SUPERVISION  BY 

Franklin  A. McCann 

ENTITLED A_  7.  _9  A _ _?  ®_  _ PJt  _ 0.Q  §>1  _ C).b  t_a  i ne  d _ Ijy 

the  Use  of  Benzene  and  Toluene  Under  High  Pressure. 

IS  APPROVED  BY  ME  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR  THE 
DEGREE  OF Bachelor__Qi._SjiiejQc.e 


College  of  Liberal  Atrs  and  Sciences 


Approve] 


ACTING  HEAD  OF  DEPARTMENT  OF  -CHEMISTRY. 


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TABLE  OF  CONTENTS 


T.  Introduction 

1.  Nature  of  the  problem,#, 3 

2*  Historical 4 

3«  Theoretical 8 


III.  Experimental 

1.  Apparatus 9 

2.  Determination  of  the  products...*  10 

III.  Results...*. 11 

IV  Discussion  of  Results 18 

V.  Summary * 21 

VI.  Bibliography 22 


Digitized  by  the  Internet  Archive 
in  2016 


https://archive.org/details/studyofproductsoOOmcca 


APPRECIATION 


This  work  was  done  under  the  direction 
of  Dr. T. E.Iayng,  who  has  given  advice, 
help,  and  instruction  throughout  this 
investigation.  I am  deeply  Indebted  to 
him,  not  only  for  the  assistance  he  has 
given,  but  for  the  inspiration  he  has 
been  throughout  the  year. 


5 


A STUDY  OF  THE  PRODUCTS  OF  COAL 
OBTAINED  BY  THE  USE  OF  BICNZENE 
AND  TOLUENE  UNDER  HIGH  PRESSURE. 

I.  Introduction. 

1.  Nature  of  the  problem. 

The  study  of  coal  by  the  use  of  solvents  is  not  a new  one. 
Organic  solvents,  to  be  true  solvents,  as  distinct  from 
reagents,  should  be  chemically  inert  towards  both  the 
the  substances  extracted  and  the  residue.  This  is  why 
the  present  work  has  been  carried  on  with  benzene. 

Benzene  has  been  used  many  times  before  but  always  with 
low  yields.  The  primary  object  therefore  has  been  to 
find  some  means  by  ^ich  benzene  can  be  made  to  give 
good  yields.  High  temperatures  and  pressures  were  tried, 
and  excellent  results  were  obtained. 

Another  object  of  this  work,  and  the  ultimate  aim,  has 
been  to  throw  some  light  upon  the  reason,  and  process 
of  coal  during  carbonization.  By  studying  the  fractions 
of  coal  obtained,  and  their  behavior  in  carbonizing,  a 
better  insight  can  be  gained  into  the  properties  of 
resins  (extracted  material)  and  the  cellulose  or  humic 
bodies  (residue)  • 

The  best  solvents  up  to  this  time,  notably  pyridine  and 


4 


phenol,  undoubtedly  perform  more  than  a solvent  action. 

In  this  particular  benzene  has  untold  advantages,  as  it 
is  strictly  neutral,  and  affects  neither  the  extract  nor 
the  residue.  Benzene  has  been  held  in  dififavor  because  of 
its  low  solvent  action  on  coal,  the  use  of  high  temperature 
and  pressure  however  removes  this  objection  and  places 
benzene  among  the  best  of  the  true  solvents. 

2.  Historical. 

Schrotter*  y^as  the  first  to  study  coal  with  the  use  of 
solvents,  he  began  his  work  in  1849.  Lei sesse*  al so  worked 
with  solvents  in  18  57,  but  these  studies  were  isolated 
and  without  much  value.  The  first  systematic  study  was 
made  by  De  Marsilly' in  1862.  He  treated  coal  with  alcohol, 
ether,  carbon  disulfide,  benzene,  and  chloroform  at  their 
boiling  points.  He  found  that  chloroform  was  the  best.  This 
is  the  first  record  of  benzene  being  used  as  a solvent. 

De  Marsilly  was  also  the  first  man  to  use  pressure  work 
for  extracting  coal.  He  tried  benzene  and  chloroform 
under  fifteen  pounds  pressure  in  a Papin's  digester.  He 
found  no  increase  in  solvent  action. 

Guignet]  1879,  made  the  first  extraction  that  gave  a good 
yield,  dry  phenol  extracting  4^c*  This  gave  a brown  solution. 
Dondorf fl  in  1881,  obtained  a brown  resin,  using  ether, 
which  gave  a yield  of  .3^.  Londorff  was  the  first  olffserver 
of  the  fluoresence  of  extract  solutions.  The  terra  resin 


’ 5 

may  cause  some  confusion,  by  it  is  meant  any  amorphous, 
vitreous  mass  of  organic  compounds  of  inde terminal  com- 
■ position. 

Siepmann^  1891,  using  ether  in  a Soxhlet  apparatus,  on  a 
West]phalian  coal  obtained  a deep  brown  solution  with  a 
green  fluoresence.  The  extract  was  1.25^.  The  year  1891 
also  records  another  failure  of  benzene,  Watson  Smith' 
tried  several  coals  with  yields  of  less  than  one  percent. 
With  pyridine  he  obtained  a yield  of  20,^c 

Pictet  and  Ramseyer' in  1911,  i sol ated  hexahjrdrofluorene, 
Gi3Hi6>  from  a benzene  soluble  extract.  These  men  are  now 
working  with  benzene  on  an  elaborate  scale,  in  1918  ex- 
tracting 5.5  tons  of  coal  with  benzene  at  its  boiling 
point  for  four  days.  They  obtained  ten  and  one-half  kilos 
of  concentrated  heavy  brown  solution,  refraining  from 
completely  drying  it. 

The  work  done  on  carbonization  of  the  portions  of  coal 
has  been  comparatively  late;  the  notable  workers  in  this 
1 ine  are  Burgess  ana  V/heeler,  Parr  and  Hadley,  and  Porter 
and  Taylor. 

Burgess  and  Wheelerlargue  that  coal  contains  two  types 
of  compounds  of  different  degrees  of  ease  of  decompostion: 
The  one,  the  least  stable,  yielding  the  parrafin  hydro- 
carbons and  no  hydrogen;  the  other  decomposing  with  great- 
er difficulty  and  yielding  hydrogen  alone,  or  possibly 


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6 

hydrogen  and  the  oxides  of  carbon,  as  its  decomposttion 
products. 

Porter  and  Taylor^di sagree  with  Burgess  and  Wheeler  and 
find  that  the  cellulosic  portion  decomposes  first,  this 
is  the  constituent  that  the  latter  claim  decomposes  last, 
yielding  hydrogen.  Porter  and  Taylor  found  that  the  cell- 
ulose broke  down  into  water,  the  oxides  of  carbon,  and 
hydrocarbons. 

Jones  and  Wheeler  "^studied  the  decomposition  of  the  sol- 
uble and  insoluble  portions  of  coal  usinf  pyridine  as  a 
solvent.  Ihe  cellulosic  portion,  or  residue  yielded 
chiefly  phenolic  products.  ITie  resinic  portion,  the  extract, 
yielded  some  phenolic  products  and  hydrocarbons.  They 
contented  themselves  chiefly  with  the  tars  obtained. 

Parr  and  HadleyJused  a comparatively  high  temperature  in 
distilling  their  fractions,  800  deg.:  phenol  was  used  as 
a solvent.  The  marked  differences  in  the  gases  evolved 
were  an  increase  in  hydrogen  in  the  cellulose,  or  residue, 
and  more  paraffins  in  the  extract. 

Later  work  has  been  done  on  carbonization  especially  in 
its  relation  to  low  temperature  carbonization,  by  Parr 
and  Layng  at  the  University  of  Tllinoi s.^They  find  that 
the  order  of  evolution  of  gases  is  as  follows*  v/ater  250  to 
300,  carbon  dioxide  300  to  350  deg.,  and  methane  350  to 
4pp  deg.  At  this  stage  begins  the  evolution  of  ethane  and 


7 


the  heavier  hydrocarbons.  They  also  find  that  the  sulfur 
that  is  organically  combined  begins  its  early  discharge# 
and  the  sulfur  in  the  form  of  pyrites  does  not  decompose 
until  much  higher  temperatures  are  reached.  The  pyritic 
sulfur  shows  itself  chiefly  in  the  tars. 

Both  Parr  and  Layng,  and  Potter  and  Taylor  find  that  most 
of  the  organic  material  of  coal  is  broken  down  at  an 
early  stage  in  heating,  below  500  deg. 

Layng'^advances  a theory  in  regard  to  the  oxidation  or 
weathering  of  some  coals  more  than  others.  He  states 
that  the  peculiar  stratifications  of  resins  and  cell- 
ulose in  Eastern  bituminous  coals  is  the  cause  for 
their  non** weathering  as  fast  as  an  Illinois  coal  where 
the  resins  and  cellulose  are  scattered.  The  resins  act 
as  a protective  coating  for  the  readily  oxidizable  cell- 
ulosic  portions,  while  in  the  Illinois  coal  due  to  this 
scattered  protection  the  cellulose  is  quickl«y  weathered. 


8 


3.  TheErretical- 

There  are  several  theories  as  to  the  coking  of  coal, hat 
the  one  most  generally  accepted  is  that  a pasty  layer 
forms  around  the  hot  walls  and  travels  slowly  inward  to 
the  center  of  the  coal  mass,  coking  the  coal  as  it  travels* 
The  gases  are  thought  to  eacape  from  the  humus  bodies 
first,  and  are  followed  by  the  decomposition  of  the  resins, 
which  leave  a pitch  behind,  binding  the  coke.  If  this  is 
true  an  analysis  of  the  gases  from  the  extract  and  the 
residue  should  show  evidences  of  this  priority  of  de- 
composi tion* 

Many  experimenters  have  extracted  the  resins  from  the 
coal  and  afterwards  worked  with  the  coal  fractions.  This 
vyork  seems  to  bear  out  the  theory  that  the  resins  cause 
the  coking,  as  the  residue  left  after  an  extraction  will 
not  coke,  while  the  extract  or  a mixture  of  the  extract 
and  the  residue  will. 

The  hydrogen  to  oxygen  ratio  in  coal  is  also  an  index 
to  the  coking  of  coal.  An  ultimate  analysis  of  the 
products  of  coal  should  then  throw  some  light  on  the 
causes  for  coking  as  the  extract  and  residue  have  differ- 
ent ratios. 

We  are  then  faced  with  the  following  problems: 

1)  fthat  is  the  best  way  to  obtain  a good  yield  with 


9 


a strictly  neutaal  sol]»ent? 

2)  In  v/hat  way,  if  any,  do  the  extract  and  residue  differ 
from  the  original  coal?  Does  this  difference  affect  the 
coking  properties? 

3)  UShat  effect  has  the  resin  to  cellulose  ratio  have  in 
coking  coals?  Ihe  hydrogen  to  oxygen  ratio? 

4)  What  form  of  sulfur,  organic  or  inorganic,  causes 
the  evolution  of  hydrogen  sulfide? 

II.  Experimental. 

1.  Apparatus. 

An  iron  pressure  bomb  was  used  for  all  extractions.  Tni s 
7/as  merely  an  old  mercury  flask  with  a screw  plug  at  the 
top.  This  plug  was  treated  with  a mixture  of  litharge  and 
glycerine  before  each  extraction,  so  as  to  better  seal  the 
plug. 

The  heating  devise  was  an  electric  furnace  wound  with  ni- 
chromc  resistance  wire.  The  temperature  control  was  effected 
by  a sliding  resistance  wire. 

The  fractional  carbonization  apparatus  consisted  of  a 
glass  flask  for  the  coal,  a tube  for  catching  the  tar  and 
water,  and  a tube  filled  with  cadmium  sulfate  to  absorb 
the  hydrogen  sulfide  evolved,  and  two  sets  of  aspirator 
bottles  to  contain  the  gases  delivered.  Tlie  heating  was 
accomplished  by  a small  electric  furnace,  the  temperature 


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control  was  obtained  by  resistance  wire.  The  temperature 
of  the  flask  was  measured  by  a 500  deg  nitrogen  filled 
thermometer. 

2.  Determination  of  products. 

The  coal  after  extraction  was  filtered  and  the  undissolved 
coal  put  back  into  the  flask  together  with  more  solvent 
for  a further  extraction.  The  solution  was  refiltered  and 
distilled  until  a thick  brovn  solution  resulted.  This  sol- 
lution  was  brom  by  transmitted  light  and  green  by  reflected 
light.  It  was  then  transferred  to  a storage  bottle,  prev©* 
lously  weighed,  and  the  remaining  benzene  evaporated  at 
100  deg.  Nitrogen  was  passed  in  during  this  last  concen- 
tration and  the  bottle  sealed.  Air  however  had  little  ef- 
fect on  the  extract  and  it  is  doubtful  if  this  precai&tion 
was  necessaaby.  The  residue,  or  undissolved  coal,  after  the 
last  extraction  was  Flashed  with  alcohol  and  ether  and 
sealed  in  nitrogen.  Air  attacks  the  residue  with  great 
avidity  and  it  is  necessary  to  keep  the  residue  in  the 
presence  of  some  inert  gas. 

The  analysis  of  the  products  was  as  follov/sJ  for  carbon, 
the  coal  was  fused  with  sodium  peroxide  and  treated  with 
acid,  the  evolved  carbon  dioxide  was  measiured  and  absorbed 
in  caustic  potash.  The  air  in  the  mixture  was  measured  and 
deducted  from  the  total  gas.  From  the  volume  of  carbon 
dioxide,  the  temperature,  and  the  pressure,  the  total 
carbon  in  the  coal,  extract,  and  residue  was  determined. 


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11 

Sulfur  was  determined  by  fusion  with  sodikum  peroxide 
and  precipi tation  with  barium  chloride.  Nitrogen  was 
determined  by  the  well  known  Kjeldahl  method.  The  hydrogen 
was  found  by  Eu  Long's  formula  after  the  B.t.u*  was  det- 
ei'mined  with  an  oxygen  bomb  calorimeter.  Oxygen  was  found 
by  difference. 

The  gases  from  the  fractional  carbonization  were  analyzed 
by  a modified  Ordat  gas  apparatus.  The  carbon  dioxide  was 
absorbed  by  caustic  potash,  the  oxygen  by  alkaline  pyro- 
galloi,  the  unsaturated  hydrocarbons  by  bromine  water,  the 
aromatics  by  firming  sulfuric  acid,  the  hydrogen  and  carbon 
monoxide  were  oxidized  in  a copper  oxide  furnace,  the  con- 
traction being  the  hydrogen,  and  the  carbon  dioxide  formed 
absorbed  by  caustic  potash  and  this  volume  is  the  carbon 
monoxide.  The  remaining  products  are  then  burned  in  a 
mercury  bulb  in  the  presence  of  oxygen  in  excess,  and  the 
paraffins  computed  from  the  loss  in  volume  and  the  amount 
of  carbon  dioxide  formed. 

ITT.  Results. 

Benzene  was  found  to  extract  13^  from  the  coal.  The  sol- 
ution was  a port  wine  color  by  transmitted  light  and  green 
by  reflected  light.  Wien  evaporated  to  dryness  the  extract 
was  hard  and  vitreous. 

Various  amounts  of  coal  and  benzene  were  tried  but  the 


12 

bext  results  were  obtained  by  using  twenty -five  grams  of 
coal  and  two  liters  of  benzene.  Two  extractions  were 
sufficient  when  tliese  amounts  were  used.  Hie  temperature 
used  was  273  deg  #iich  gave  50  atmospheres  pressures,  the 
critical  temperature  and  pressure  of  benzene. 

Toiiiuene  was  used  and  a twenty-five  percent  extraction  of 
the  coal  obtained.  The  dried  extract  was  not  resinous 
however,  and  therefore  not  as  satisfactory  as  benzene  which 
seems  to  be  an  ideal  solvent. 

The  coal  used  was  £rom  the  Fairmount  district  of  West 
Virginia,  and  had  the  following  proximate  analysis. 

As  received  basis. 

Moisture  2.3^ 

Volatile  Matter  36.7^c 
Ash  5.8^ 

Fixed  Carbon  55.  2% 

The  ultimate  analyses  of  the  original  coal,  extract,  and 
residue  are  given  in  tables  5 and  II. 


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15 

Praotional  Carboni zation. 

The  apparatus  was  put  under  a vacuum  of  three  feet  of 
water,  exhausted,  filled  with  nitrogen,  and  exhausted 
again.  Tiiis  was  done  repeatedly  until  all  the  air  was 
expelled  and  the  coiil  and  apparatus  saturated  with  nit- 
rogen. 

Ten  grams  were  used  as  a charge.  The  coal  was  carbonized 
’*as  teoeived’*.  The  flask  was  slowly  heated  and  a out 
of  the  gases  made  at  350  deg  and  another  at  450  deg.  iiere 
the  carbonization  was  stopped.  The  tar  of  the  original 
coal  was  black  and  heav^,  of  the  residue  black  atid  light, 
and  the  extract  of  thennature  of  a light  oil,  it  was 
reddish  in  color  and  accompanied  by  a red  wax  which  did 
not  mix  with  the  oil  evolved. 

The  analyses  of  the  two  cuts  of  gases,  the  amount  of 
tar  and  hydrogen  sulfide  evolved,  for  the  driginal  coal, 
extract,  and  residue  will  be  found  in  tables  III  and  IV. 


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IV.  Discmssi  on. 

Benzene  extracts  13^  material  of  a resinous  material 
from  coal  when  used  under  high  temperatures  and  pressures. 
The  residue  consists  of  the  ash,  undissolved  resins,  and 
the  material  of  cellulosic  nature. 

An  ultimate  analysis  of  the  produats  shows  that  neither 
the  extract  nor  the  residue  is  chemiaally  affected  by 
the  action  of  the  benzene. 

This  ultimate  analysis  shows  that  the  ratio  of  hydrogen 
to  oxygen  is  approximately  5.5  to  6.5  in  the  original 
coal,  5 to  6 in  the  extract,  and  5*  5 to  7 in  the  residue. 

If  we  accept  the  theoty  of  the  hydrogen  to  oxygen  ration 
as  an  index  to  coking  coals,  the  residue  should  give  the 
poorest  coke.  This  was  found  to  be  the  case.  The  reason 
for  the  residue  coking  at  all  was  because  of  some  un- 
dissolved resins  which  had  not  been  extracted  by  the 
benzene.  The  residue  form  the  toluene  extraction,  which 
gave  a better  yield,  and  therefore  extracted  more  resins, 
gave  only  a powder  -when  given  coking  tests. 

Cherry ‘^found  that  coal  absorbs  oxygen  readily  but  states 
that  little  is  evolved  as  carbon  dioxide.  The  carbonization 
of  the  residue,  which  is  the  portion  which  absorbs  oxygen, 
showred  a great  evolution  of  carbon  dioxide,  though  it 
was  exposed  to  the  air  but  a shoijt  time. 


19 


Burgess  and  Wheeler^argue  that  the  resins  decompose  first 
and  the  cellulosic  material  with  greateji  difficulty  and 
yielding  only  hydrogen  and  the  oxides  of  carbon.  The  car- 
bonization of  the  coal  fractions  shows  that  the  cellulose 
begins  to  decompose  earlier  th>an  350  deg  and  with  the  for- 
mation of  paraffins  to  the  extent  of  36^  of  the  gas  evol- 
ved at  350  deg.,  and  52^  paraffins  at  450  deg.  The  volume 
of  gas  evolved  from  each  of  the  products  shows  a greater 
ease  in  the  decomposition  of  the  resins,  and  jn  this  res- 
pect substantiating  Burgess  and  V.'heeler  who  find  that  the 
resins  are  the  easier  decomposed  of  the  two. 

Porter  and  Taylor^^claim  that  the  cellulosic  derivatives 
decompose  the  more  easily,  forming  water,  the  oxides  of 
carbon,  and  hydrocarbons.  The  results  obtained  cannot 
entirely  substantiate  this,  as  the  resinic  extract  de- 
composed much  more  readily.  The  presence  of  hydrocarbons 
in  the  residue  decomposition  bear  out  their  ^statements 
as  against  Burgess  and  fl,heeler,  who  claim  that  the  cellu- 
losic |)ortion  gives  only  hydrogen  and  the  oxides  of  carbon. 

The  great  amount  of  hydrogen  sulfide  evolved  from  the 
resinous  extract  agrees  with  Parr  and  Layng'^who  find 
that  the  sulfur  organically  combined  is  evolved  at  an 
early  stage.  It  also  shows  that  the  evolution  of  hydro- 
gen sulfide  is  due  to  the  organic  sulfur  and  not  the 
pyrites. 


20 


A study  of  th^  carbonization  also  points  out  clearly  the 
effect  of  weathering  on  coal.  The  best  coal  to  weather 
or  store  is  an  Eastern  bituminous,  the  coal  worked  with, 
which  has  the  resins  and  cellulose  in  stratified  form. 

It  is  thought  that  the  resins  in  this  form  of  layer  pro- 
tection prevent  the  cellulosic  portion  from  being  oxidized. 
If  the  coating  d)f  tesin  is  takeri  away,  as  is  the  case  in 
extraction,  the  cellulose  is  no  longer  protented  by  the 
resin  and  oxidizes  rapidly.  The  residue  yielded  29^  more 
carbon  dioxide,  notwithstanding  the  precautions  to  protect 
it  with  nitrogen,  than  the  residwe.  This  proves  that  the 
resin  is  undoubtedly  is  a protecting  agent. 


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21 


V . Sunni  ary . 

1)  Benzene  proves  an  efficient  solvent  for  coal  if  used 
under  high  temperature  and  pressure. 

2)  The  action  on  the  coal  is  of  a tru,e  solvent  nature 

as  neither  the  extract  nor  the  residue  is  chemi sally 
affected. 

3^  The  residue,  or  cellulosic  portion,  shows  a great  avidity 
for  oxygen,  which  it  absorbs  rapidly,  and  gives  up 
on  heating  as  carbon  dioxide.  In  this  respect  it 
resembles  activated  carbon. 

4)  'Ihe  resinous  portion  of  the  coal  is  the  material 
which  decomposes  most  easily,  giving  hydrogen,  the 
oxides  o§  carbon,  and  hydrocarbons. 

5)  Tlie  cellulosic  portion  decomposes  eatly  but  not  as 

easily  as  the  resins,  giving  hydrogen,  the  oxides 
of  carbon,  and  hydrocarbons. 

6)  Hydrogen  sulfide  is  evolved  by  the  organic  sulfur 
in  coal  rather  than  by  the  inorgan^  c. 

7)  The  resinic  material  proves  a protecting  agent  for 
the  cellulose,  if  the  two  are  in  stratified  form.  If 
the  resin  is  removed,  the  cellulose  oxidizes  easily. 


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22 


VI.  Bibliography. 


1« 


2 

3 

4 

5 


7 


Constitution  of  Goal*«^  Stopes  and  Wheeler-  1918. 

"Goal  and  its  Scienticio  Uses”-  Bone. 

"The  .dialysis  Of  Coal  witn  Phenol  as  a Solvent"  Parr-Hadley 
The  Effect  of  Oxygen  on  the  Coking  of  Goal"  Cherry 
"Low  Temperature  Carbonization  ond  its  Application 
to  High  Oxygen  Goals"  Parr  and  Layng-J . I.  E.  Chem  1921. 
Porter  and  Taylor,  "The  Primary  Volatile  Products  of 
the  Carbonization  of  Coal"  Eept.  of  Int.  bull  ^^^140 
T.E.Layng,  by  oral  communication. 


